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Alkaline Depolymerization of Polyethylene Terephthalate Plastic Waste

Article  in  Tikrit Journal of Engineering Sciences · June 2014

DOI: 10.25130/tjes.v22i1.334

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 Ammar S. Abbas/Tikrit Journal of Engineering Sciences 21(2) (2014)1-8 1

ISSN: 1813-162X
Tikrit Journal of Engineering Sciences
available online at: http://www.tj-es.com

Alkaline Depolymerization of Polyethylene Terephthalate Plastic Waste

Ammar S. Abbas
Chemical Engineering Department, College of Engineering, University of Baghdad

(Received 09 July 2013, Accepted 12 January 2014, Available online 5 June 2014)

ABSTRACT
Depolymerization reaction is considered one of the most significant ways of converting waste
polyethylene terephthalate in to terephthalic acid. The water polyethylene terephthalate bottle waste was
collected from different places in Baghdad. The collection step shows that there is plenty amount of
polyethylene terephthalate suitable to be an important source of terephthalic acid production.
PET plastic waste conversion to terephthalic acid by depolymerization process was examined.
The effect of ethylene glycol amount, reaction time (up to 90 minutes) and reaction
temperature (from 70 to 170° C) on the polyethylene terephthalate conversion was obtained.
The kinetic study shows that the ordination of the depolymerization reaction of PET is first
order irreversible reaction with 31103.5 J/mole activation energy.
A 97.9 % terephthalic acid purity has been obtained by purification with N, N-
dimethylformamide.
Keywords: Depolymerization, Polyethylene terephthalate plastic, Terephthalic acid, Kinetic study,
Domestic municipality waste.

‫التحلل القلوي لمخلفات البولي أثلين البالستيكية‬

‫الخالصة‬
‫ت ات عيررر اعتدلررر اا ررر فا وعررر ا‬. ‫يعتبرررفاتل ارررلا وتحدرررلال حرررلاعرررةا وحرررفما وععتبرررفااوتحليرررلاعتدلررر اابرررلوفا لدررريةاتفيل ويررراا وررر احررر ع ا وتفيل ويررر‬
‫ا رر فاا رر ا وتحررلاا ورر اتررليفاوعيرر اال يررفااعررةابك ررتي ابررلوفا‬.‫وعصرر لاماعررةابك ررتي ابررلوفا لدرريةاتفيل ويررااعررةاع رر حماعتلف ررماعررةاب ررل ل‬
‫ تعررراالف رررماتل ارررلا وتحديررررلاوبك رررتي ابرررلوفا لدررريةاتفيل ويررراا ورررر ا‬.‫لدررريةاتفيل ويررراالا وررر صايعتبرررفاعصرررلفاعلرررر اي تررر احررر ع ا وتفيل ويرررا‬
‫ال يقرررم الالف رررماحررررف فاا‬09‫الاتررر ا وحصرررللاادرررر اتررردليفاورررلاعرررةاوعيررررمال رررللا يلدررريةاوكيورررللالا عرررةا وتل اررررلا حتررر ا‬.‫حررر ع ا وتفيل ويرررا‬
‫ لف رررماحفويرررما وتل ارررلا ررر فاا وررر ا ةا وتل ارررلا‬.‫الف رررماعةليرررم اادررر اتحرررللابك رررتي ابرررلوفا لدررريةاتفيل ويرررا‬009‫الاحتررر ا‬09‫وتل ارررلا عرررةا‬
‫ ترر ا وحصرررللاادرر احرر ع ا وتفيل ويرررااب قرر لااعقرررل ف ا‬.‫ا رررللاووررلاعررلل‬31103.5‫غيررفااو ررفالاعرررةا ولف ررما يلورر ابح رررمات رريحاعقررل ف ا‬
.‫ابعلات قيتهاب ول صاعيل يلايلفع ع يل‬%‫ا‬00.0
.‫ النفايات البلدية المحلية‬،‫ دراسة الحركية‬،‫ حامض الترفثالك‬،‫ ب الستك البولي اثلين ترفثاليت‬،‫ تفاعل التحلل‬:‫الكلمات الدالة‬

Abbreviations : The depolymerization reaction activation

EG: Ethylene glycol. energy (J/mole).
PET: Polyethylene terephthalate.
: The depolymerization reaction coefficient
pTPA: Producing terephthalic acid.
sTPA: Standard terephthalic acid. (min).
TPA: Terephthalic acid. : The frequency factor of the Arrhenius
Nomenclatures equation (min).
: The concentration of PET. : The Universal gas constant (8.314
: The initial concentration of PET. J/mole.K).
: The PET depolymerization reaction rate
(mole/min).
 Ammar S. Abbas/Tikrit Journal of Engineering Sciences 21(2) (2014)1-8
: The depolymerization reaction time (min).
: The depolymerization reaction temperature
(K).
: The PET conversion (calculated from
Eq. 1).
Introduction
Through the resent years, plastics
portion in the municipal solid waste increases
dramatically. Plastics are occupied between 5
to 15 wt.% (20 to 30 vol. %) of municipal solid
waste [1].
Most plastics are non-degradable and
possibly take hundred years to decompose
naturally.
The published statistics for Western
Europe estimate the yearly consumption of
plastic products about 100 kg per person for a
total of over 39.1 million tones [2]. Over 78
wt.% of this total corresponds to
thermoplastics such as high density
polyethylene (HDPE), low density polyethylene
(LDPE), polypropylene (PP), poly-vinyl
chloride (PVC) and polyethylene terephthalate
(PET). The remaining 22 wt.% to thermosets
(mainly epoxy resins and polyurethane) [3].
In Arab countries (Saudi Arabia as an
example), the amount of plastic waste is about
15 wt. % in the domestic municipality waste
[4].According to the report of Jackson and
Bertényi [5], each three tons of plastic waste
contain about one ton of PET which equal to
20000 PET bottles.
The depolymerization of PET was
conducted by various alcohols with sodium
hydroxide under atmospheric pressure. PET
was depolymerized to EG and disodium
terephthalate (Na2-TPA). The
depolymerization reaction is illustrated in
Figure 1.
Fig.1,Depolymerization reaction of PET [6]
The depolymerization reaction of PET
is a kind of trans-esterification reaction
2
triggered by the addition of alcohol under basic
conditions. Transesterification is the process
of substituting the alkoxyl group of an ester
compound with that of an alcohol [6].
Oku et al. [7] was produced
terephthalic acid from PET by reacting it with
NaOH solution at boiling point of the reaction
mixture (about 200°C). The result show that
terephthalic acid can be produced at this
temperature within 20 minutes the produced
mixture after that washed by water firstly
followed by H2SO4 solution and then water
again.
Ben-Zn Wan et al. [8] made hydrolytic
depolymerization of PET flakes in a potassium
hydroxide solution. The reaction was carried
out in a stirred batch reactor at 120, 140 and
160° C for 30 minutes and under pressure of
about 1.7, 2.9 and 4.9 atm. Zinc acetate was
used as catalyst in the reaction with sulfuric
acid into the filtrate to neutralize the potassium
hydroxide and TPA produced was by water.
Abbas et al. [9], reported that the maximum
yield of terephthalic acid from PET by the
depolymerization reaction in the presence of
ethylene glycol can be obtained at 40 minutes
and 170°C.
Yusuke Asakuma et al. [6], studied the
depolymerization reaction of virgin PET bottles
on the basis of both experimental data and
numerical data obtained from quantum
chemistry calculations. Various alcohols were
used as solvents in the search for the reaction
mechanism. The maximum PET conversion
through the depolymerization reaction in
presence of ethylene glycol was about 30% at
78°C after 3 hours.
The present work, was intended
to study the depolymerization reaction of
collecting waste PET bottles with NaOH in
order to produce terephthalic acid. The
effects of the initial amount of ethylene
glycol, reaction temperature and time
were considered.
Experimental Work
Materials
1. PET bottle waste, collected from different
places in Baghdad, was used. Water
bottles with thickness 0.4 mm and density
is 1.18 g/cm3.
 Ammar S. Abbas/Tikrit Journal of Engineering Sciences 21(2) (2014)1-8
2. Sodium hydroxide (NaOH): NaOH
molecular weight 40 and purity of 99.8%.
(RIEDELDEHAEN AG
SEELZEHANNOVER Chem. rian,
plozchen, DAB7, B.P.1968 M.Wt. 40)
3. Ethylene glycol (C2H6O2), BDH Chemicals
Ltd.
4. Sulfuric acid: H2SO4 of molecular weight of
98.07 and specific gravity of 1.84 was
used.
5. N, N-dimethylformamide (DMF):‫ ا‬DMF
(C3H7NO) of molecular weight 73.10 was
used as purification agent because of its
highly selective dissolver of terephthalic
acid rather than by product of
depolymerization reaction.
6. Standard terephthalic acid: Terephthalic
acid of 98.3 % purity was used as
standard. The standard terephthalic acid is
from Aldrich Chemical Co. Ltd.
Apparatus
The apparatus used in this study for
depolymerization (saponification) reaction in a
batch scale system consists of the followings:
1. 3 Necks flask (500 ml).
2. Heat flat magnetic stirrer (Stuart
CB302 / USA).
3. Reflux Condenser (Germany), 37 cm.
4. Mercury thermometer from zero to
250 °C.
Depolymerization of PET procedure
50 g of waste PET flakes of the
dimension of about 5*5*0.4 mm, with 25 g of
NaOH (about 20% excess of the stoichiometric
amount) and different amounts of ethylene
glycol (200, 300 and 400 ml) were entered in a
flask under atmospheric pressure. The mixture
was heated to 70 to 170°C with stirring. A
sample of the reaction mixture was used up
(every 15 minutes) and pour directly in a 20 ml
of distilled water of room temperature to stop
the reaction, and the unreacted PET was
filtered. Furthermore, a small amount of H2SO4
was added until neutralized to the filtrate, and
the terephthalic acid (TPA) was precipitated.
Conversion of PET through reaction
was calculated as:
3
…1
In order to purification of TPA, the
precipitated amount of TPA was filtered and
then dried in oven at 85 °C overnight to get rid
of the moisture. The produced dry TPA was
dissolved in DMF, the un-dissolved materials
were removed by filtration and TPA is
recovered by evaporation of DMF. The
characterization tests of producing TPA were
compared with those for standard TPA.
Testing methods
Final produce terephthalic acid sample
was tested for:
1. Melting point: according to ASTM D-127-
05, the test was done in the Ministry of
Industry and Minerals, General
Commission for Research and Industrial
Development, Chemical and
Petrochemical Research Center.
2. Acid number: according to ASTM D664-
06, the test was done in the Ministry of
Industry and Minerals, General
Commission for Research and Industrial
Development, Chemical and
Petrochemical Research Center.
3. Ash residue: according to ASTM D1951-
86, the test was performed at the
University of Baghdad, College of
Engineering, Chemical Engineering
Department.
4. Infra-red (IR) analysis: IR-scan, with
wavelength between 4000 and 400, for
producing TPA was accomplished by IR-
spectrophotometer made by Shimadzu of
model FTIR-8400S. This test was done in
the Central Organization of
Standardization and Quality Control.
Results and Discussion
Collection of PET bottles waste
PET bottles were collected from
different places in Baghdad (Iraq), these
places were 17 houses from different
neighborhoods of the capital Baghdad, 1
kindergarten, and 1 coffee-shop. These places
serve about 397 persons per day. The
collection was done in different days in March
and April, 2013.
 Ammar S. Abbas/Tikrit Journal of Engineering Sciences 21(2) (2014)1-8 4

Table 1 shows the classification and is very close to the reported estimation values
weight of the collected PET bottles, while of Western Europe and Saudi Arabia [2, 3].
Table 2 summarized the places, numbers of
persons and the average collected waste Effect of EG on the PET conversion
bottles per days. The effect of EG on the PET
depolymerization was intended at 90 minutes
Table 1, Classification and weight of PET of reaction time and at different reaction
waste bottles collected in Baghdad per day temperatures: 70, 130 and 170 °C.
Kinder Coffee- The results (Figure 2) show, that there
Bottle size Houses
garden shop is no significant effect of the EG on the
conversion of PET through the
0.3 L 23 70 -
depolymerization reaction.
0.5 L 55 46 -

0.6 L 68 15 208 1.0

1.0 L 5 - - 0.8

PET conversion, -
1.5 L 24 1 34
0.6

Total No. 175 132 242

0.4
Weight, kg 2.104 1.050 3.165
0.2 o
T = 70 C
o
T = 130 C
Table 2, Numbers of PET waste bottles o
T = 170 C
Reaction time = 90 minutes
collected in Baghdad per day 0.0
150 200 250 300 350 400 450
Avg.
Ethylen glycol volume (ml) per 50 g of PET feed
No. No. Weight,
Place
person PET kg
bottles Fig.2, Effect of the ethylene glycol on PET
conversion of different temperature and at 90
Houses 93 175 2.104 minutes reaction time
Kindergarten 104 132 1.050
The addition more amount of
Coffee-shop 200* 242 3.165 produced material (EG) did not cause
significant change in PET conversion or did
Total weight, kg 6.319 not change the backward reaction or
decreased the forward reaction of the
Average PET waste per person, g 15.92
depolymerization of PET. Thus,
*Approximate average number of customers depolymerization reaction shown in Figure 1
can be considered as irreversible reaction.
The average weight of PET waste per
This result is in good agreement of Yusuke
person (15.92 g) means 509.44 tons per day
Asakuma et al. [6], and it’s reinforced the next
for Iraq (Iraq population is approximately 32
assumption of being the depolymerization
million persons). This huge amount of only one
reaction of PET irreversible reaction.
single type of plastics (PET) causes an
environmental nightmare for any country. But
Effect of reaction temperature on the PET
when the filled half of the cup seen, this
conversion
massive amount of PET plastic waste is
Figure 3 shows the effect of the
considered a plenty sources for different
depolymerization reaction time and reaction
chemicals production such as terephthalic
temperature on the conversion of PET.
acid.
As shown in Figure 3, the PET
The estimation results of PET waste
conversion increase with reaction temperature
amount in Iraq, about 5.8 kg per person yearly,
and reach the highest value (0.99) at 170 °C.
 Ammar S. Abbas/Tikrit Journal of Engineering Sciences 21(2) (2014)1-8 5

While, the conversions at 70 °C were 0.04 aqueous phase and form the di-sodium
during the first 15 minutes of reaction time and terephthalate salt with NA+ [12].
0.35 after 90 minutes of reaction.
Kinetic model of PET depolymerization
o
reaction
T= 70 C
T=
o
90 C
o
The kinetic of PET depolymerization
1.0 T= 110 C
T= 130 C
o

o
was studied by assuming that the reaction is
T= 150 C
0.8 T= 170 C
o
irreversible homogeneous first order according
PET conversion, -

to PET.
0.6
The first order homogenous reaction
0.4
kinetic model is [13]:

0.2
...2
200 ml of ethylene glycol per 50 g of PET feed
0.0
0 20 40 60 80 100

Depolymerization reaction time (t), min.

But:

Fig.3, Effect of the depolymerization reaction ...3

time on the PET conversion of different
temperatures and 200 ml of ethylene glycol
per 50 g of PET feed ...4

These results are in good agreement The integration of Equation 4 gives the regular
with those that extracted from Abbas et al. [9] first order reaction model:
which reported that the maximum yield of
terephthalic acid (maximum conversion of
...5
PET) can be obtained at 170 °C. Yusuke
Asakuma et al. [6], that pointed the conversion
of PET through the depolymerization reaction ...6
about 10 % during the 90 minutes reaction
time and at 70 °C temperature. While,
And:
Spaseska and Civkaroska [10] found that the
above 90 TPA wt.% produced during 5 hours
in temperature range 80 to 120 °C but with ...7
presence of trioctyl methyl ammonium bromide
as a catalyst.
A marked increase in PET conversion A plot of versus , as
appeared when the temperature increases to shown in Figure 4, gives straight lines with
110 °C and above. According to the collusion zero intercepts and slopes equal to the
theory [11], when temperature increases, it
reaction coefficients ( ).
may cause an increase of molecular activity,
and in the same time, the increasing of The numerical values of
solubility of PET in EG and decreasing in depolymerization reaction coefficients versus
viscosity of solution mixture. So the molecules temperature are summarized in Table 3.
have more energy to react and more The activation energy of the reaction
probability to collisions together to accomplish and frequency factor for the first order
the reaction. homogeneous depolymerization reaction are
As the solubility of PET increasing this calculated according to the Arrhenius’
means increasing of PET macromolecules equation (Eq. 7).
which that can be easily attacked by the OH -
and then be depolymerized. After that, the
produced terephthalate anion returns to the
 Ammar S. Abbas/Tikrit Journal of Engineering Sciences 21(2) (2014)1-8 6

excess of the stoichiometric amount of NaOH

5 and in the presence of ethylene glycol is:
T= 70 oC
T= 90 oC
T= 110 oC
4 T= 130 oC
T= 150 oC
T= 170 oC

3 ...8
-ln (1-xPET)

2 -2.5

-3.0

1
-3.5

-4.0
0

ln (k)
0 20 40 60 80 100
-4.5
Depolymerization reaction time (t), min.
-5.0

Fig.4, First order kinetic model of the PET -5.5

depolymerization
-6.0
0.0022 0.0023 0.0024 0.0025 0.0026 0.0027 0.0028 0.0029 0.0030

1/T, K-1

Table 3, Values of the depolymerization

reaction coefficients versus temperature Fig.5, Arrhenius’ plot of depolymerization
Temperature, °C Temperature, K k, min. reaction of PET

70 343 0.0041 The found values of reaction

coefficients are in the same magnitude of
90 363 0.0088
those obtained by Yusuke Asakuma et al. [6],
110 383 0.0198 but the calculated activation energy of the
depolymerization reaction (31103.5 J/mole)
130 403 0.0256 differs from the reported value for the
activation energy of depolymerization reaction
150 423 0.0330
in the presence of EG that about 115 kJ/mole.
170 443 0.0530 This difference due to the wide range of the
temperature studied by the present work (70 to
170 °C) on the contrary of the study of Yusuke
The plot of versus gives Asakuma et al. [6], whose studied the
polymerization reaction of PET in presence of
straight line with slope of and intercept different alcohols, but in the narrow range of
temperature (65 to 78 °C) for depolymerization
of the value if this plot is called
reaction in presence of EG.
Arrhenius’ plot. Predicted values calculated from
Arrhenius’ plot of depolymerization the first order model of PET
reaction are shown in Figure 5. depolymerization (Eq. 5), which uses the
The value of the straight line slope of found reaction rate coefficients (Table 3),
the Arrhenius’ plot equal to -3741.1 then and experimental data are shown in
Figure 6.
the value of the activation energy of the Statistical analysis of the
depolymerization reaction of PET is 31103.5 experimental data shows that the solution
J/mole, and the intercept value is of the model (Eq. 6) is proportional to the
5.5646 then the value of the frequency factor experimental results. The statistical
of the depolymerization reaction of PET is analyses are summarized in Table 4.
The statistical analyses promote that
261.02 minutes.
the depolymerization reaction of PET with EG
The final reaction rate equation of the
behaves as homogeneous first order reaction
depolymerization reaction of PET with a 20%
 Ammar S. Abbas/Tikrit Journal of Engineering Sciences 21(2) (2014)1-8 7

with a high correlation coefficient (0.9872) and Table 5, Comparison of testing properties
low standard deviation (0.0710) and standard between producing and standard TPA
error (0.0467) for 36 observations (no. of Test pTPA sTPA
experiments).
Melting point, °C 306 304
1.0
Ash residue, ppm 13 10
Predicted PET conversion (xPET), -

0.8
Acid number, mg KOH/g 674 675
0.6

Conclusion
0.4
1. The enormous quantity of PET plastic bottle
waste (approximately 509.44 tons) throws
0.2
away in Iraq daily.
2. Ethylene glycol did not effect on the
0.0
0.0 0.2 0.4 0.6 0.8 1.0
conversion of PET through the
Real PET conversion (xPET),- depolymerization reaction with NaOH
significantly.
Fig.6, Experimental and predicted values of 3. Conversion of PET of about 99% can be
apparent rate constant by using suggested reached by depolymerization of PET waste for
model of depolymerization of PET 90 minutes at 170 °C.
4. The reaction of the PET depolymerization
Table 4, Statistical analysis of the reaction was first order according to the PET.
depolymerization of PET model 5. The activation energy of the depolymerization
Statistical analysis Value reaction was 31103.5 J/mole with 261.02
minutes as the value of frequency factor.
No. of observation 36 6. The statistical analyses strengthened that the
depolymerization reaction of PET with EG
Correlation coefficient 0.9872 behaves as homogeneous first order reaction.
Standard error 0.0467 7. The purity of the produced TPA was 97.9 %.

Standard deviation (S) 0.0710 References

Variance 0.0050
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management and plastics recycling: An
NaOH in the presence of 200 ml EG at 170 °C
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